Method for developing silver halide emulsions

ABSTRACT

A photographic developing method is described which comprises developing an exposed silver halide emulsion layer of a photographic material with an aqueous alkaline composition in the presence of a hydroxylamine developing agent and a p-phenylene diamine or p-aminophenol derivative corresponding to one of the formulas   WHEREIN:   WHEREIN: R1 stands for an alkyl group, R2 stands for alkyl or for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring, R3 stands for alkyl, and R4 stands for an alkyl group, AT MOST ONE OF R1 and R4 being substituted alkyl;   WHEREIN:   WHEREIN: EACH OF R5 and R6 stands for an alkyl group, and X1 stands for an electron-donating group; and   WHEREIN: EACH OF X2 and X3 stands for hydrogen, halogen or an electrondonating group, Y stands for OH or NH2, and R7 stands for ethylene, substituted ethylene, propylene or substituted propylene attached to the adjacent ortho-carbon atom of the benzene ring, and R8 stands for hydrogen, an alkyl group or has the same significance as R7, or R7 together with R8 and the N-atom to which they are attached from a pyrrolidine ring. The p-phenylene diamine or p-aminophenol derivative has a superadditive developing affect with the hydroxyl amine developing agent.

United States Patent 1 1 Willems 1 51 Mar. 27, 1973 [54] METHOD FORDEVELOPING SILVER HALIDE EMULSIONS [75] Inventor: Jozef Frans Willems,

' Belgium [30] Foreign Application Priority Data Oct. 27, 1969 GreatBritain ..52,565/69 52 Us. 01. ..96/29, 96/66, 96/66.3 51 Int. Cl....G03c 5/54, G036 5/30 [58] Field 61 Search ..96/66, 66 T, 55, 29

[56] 7 References Cited UNITED STATES PATENTS 3,489,566 1/1970 Anselm..96/22 2,857,274 10/1958 Land ..96/29 2,857,275 10/1958 Land ..96/293,113,866 12/1963 Land ..96/29 3,406,064 10/1968 Land ..96/29 3,576,6314/1971 Archambault.... ..96/66 3,265,499 8/1966 Willems 96/66 3,265,5028/1966 Willems ..96/66 3,549,364 12/1970 MOlSB ..96/66 PrimaryExaminer--J. Travis Brown Assistant Examiner-M. F. KelleyAttorneyBrufsky, Staas, Breiner and Halsey [57] ABSTRACT A photographicdeveloping method is described which comprises developing an exposedsilver halide emul sion layer of a photographic material with an aqueousalkaline composition in the presence of a hydroxylamine developing agentand a p-phenylene diamine or p-aminophenol derivative corresponding toone of the formulas I211 R1 N wherein:

R stands for an alkyl group,

R stands for alkyl or for ethylene, substituted ethylene, propylene orsubstituted propylene attached to the adjacent ortho-carbon atom of thebenzene ring,

R; stands for alkyl, and

R stands for an alkyl group,

at most one of R and R being substituted alkyl;

wherein:

each of R and R stands for an alkyl group, and X stands for anelectron-donating group; and

wherein:

each of X and X stands for hydrogen, halogen or an electron-donatinggroup, Y stands for OH or NH,, and R, stands for ethylene, substitutedethylene, propylene or substituted propylene attached to the adjacentortho-carbon atom of the benzene ring, and R stands for hydrogen, analkyl group or has the same significance as R or R together with R andthe N-atom to which they are attached from a pyrrolidine ring. Thep-phenylene diamine or p-aminophenol derivative has a super-additivedeveloping affect with the hydroxyl amine developing agent.

10 Claims, No Drawings METHOD FOR DEVELOPING SILVER HALIDE EMULSIONSThis invention relates to the development of photographic materialscontaining exposed silver halide, to new developing combinations and tophotographic materials and solutions containing such combinations.

It is known that certain chemical compounds, which used alone are poordevelopers for photographic silver halide emulsions, become much moreeffective when used in conjunction with other developers, the effectbeing known as superadditivity. Thus, for example it is known thatp-phenylene diamine derivatives and paminophenol derivatives show thephenomenon of superadditivity when used in conjunction with developingagents the ionized forms of which in alkaline medium carry two or morenegative charges such as hydroquinone, hydroquinone sulphonate, ascorbicacid, etc.

It has now been found that these p-phenylene diamine and p-aminophenolderivatives also exhibit a superadditive character when used inconjunction with the at most singly ionized developer anions ofhydroxylamine and derivatives thereof.

The use of hydroxylamine and derivatives thereof, of which the oxidationproducts have the favorable property of leaving no residual stain in thesilver image obtained has been disclosed amongst others in U.S. Pat. No.2,857,276 of Edwin H. Land and Helen J. Tracy issued Oct. 21, 1958.Hydroxylamine itself and the mono-alkyl derivatives are less suitablebecause they can give rise to fog but the N,N-dialkylhydroxylamines suchas N,N-diethylhydroxylamine and the heterocyclic N-hydroxylamines suchas N-hydroxymorpholine, N-hydroxypiperidine'and N-hydroxypyrrolidinedisclosed in the above United States Patent Specification areparticularly suitable. Other hydroxylamine derivatives that have beenproposed for use as silver halide developing agents and of which thedevelopment activity is higher than that of the N,N-dialkylhydroxylamines include for example aminoalkyl hydroxylamines, moreespecially N,N-dialkylhydroxylamines having in at least one of theN-alkyl groups an intralinear amino nitrogen atom, either cyclic oracyclic, examples of which can be found in U.S. Pat. No. 3,287,125 ofMilton Green, Adnan A.Sayigh and Henri Ulrich issued Nov. 22, 1966,alkoxyhydroxylamines, more especially N,N-dialkylhydroxylamines of whichat least one of the n-alkyl groups is substituted by alkoxy oralkoxyalkoxy, examples of which can be found in U.S. Pat. No. 3,293,034of Milton Green, Adnan A.Sayigh and Henri Ulrich issued Dec. 20, 1966and sulphone hydroxylamines, more especially N,N-dialkylhydroxylamineshaving in at least one of the N- alkyl groups an intralinear sulphonyl(SO,--) group, examples of which can be found in U.S. Pat. No. 3,287,124of Milton Green, Adnan A.Sayigh and Henri Ulrich issued Nov. 22, 1966.Further N,N-dialkylhydroxylamines having in at least one of the N-alkylgroups a quaternary ammonium group either cyclic or acyclic which excelby their high development activity have been proposed for use as silverhalide developing agents in the copending application filed for NovelPhotographic Developers" (=U.K. Pat. Application No. 52,564/69 filedOct. 27, 1969 by Gevaert-Agfa N.V.).

The p-phenylene diamine and p-aminophenol derivatives having asuperadditive development effect with hydroxylamine developing agentscan be represented by the following general formulae:

wherein:

each of R and R stands for alkyl including substituted alkyl e.g., alkylsubstituted as above, and

X, stands for an electron-donating group such as alkyl, alkoxy, amino,monoalkylamino, kylamino, acylamino and sulphonamido,

dial- III.

wherein:

each of X, and X stands for hydrogen, halogen such as chlorine or anelectron donating group, e.g., as exemplified for X,,

Y stands for OH or NH,, and

R stands for ethylene, substituted ethylene, propylene or substitutedpropylene attached to the adjacent ortho-carbon atom of the benzenering, and

R stands for hydrogen, alkyl including substituted alkyl for instancesubstituted as exemplified above for R or has the same significance asR, above, or

R together with R and the N-atom to which they are attached form apyrrolidine ring.

The following are representative examples of pphenylene diamine andp-aminophenol derivatives suitable for use as superadditive developingagents in conjunction with hydroxylamine a. compounds corresponding togeneral formula 1 l. 6-diethylamino-l ,2,3,4-tetrahydroquinolinedichlorohydrate 2. l-ethyl-6diethylamino-l,2,3,4-tetrahdroquinolinedichlorohydrate 3. l-(4-sulphobutyl)-6-diethylamino-l ,2,3 ,4-tetrahydroquinoline 4. l-( 2-hydroxyethyl)-6-dimethylamino-l ,2,3 ,4-tetrahydroquinoline dichlorohydrate 5. 1-ethyl-6-(N-ethyl-N-3-sulphopropylamino 1,2,3 ,4-tetrahydroquinolinedichlorohydrate 6. ll(3-sulphopropyl)-6-(N-ethyl-N-methylamino)- 1,2,3,4-tetrahydroquinoline dichlorohydrate 7.l-(2methylsulphonylaminoethyl)-6-diethylamino- 1,2,3,4-tetrahydroquinoline dichlorohydrate 8. l-( 3-carboxypropyl)-6-dimethylamino-l ,2,3 ,4- tetrahydroquinoline dichlorohydrate 9.N,N-diethyl-N',N-dimethyl-p-phenylene diamine dihydrochloride l0.N,N,N', N'-tetramethyl-p-phenylene diamine dihydrochloride l1. N,N,N',dihydrochloride l2.N,N-diethyl-N'-2-hydroxyethyl-N'-ethyl-p-phenylenediamine disulphate 13.N,N-diethyl-N'-4-sulphobutyl-N'-ethyl-p-phenylene diamine b. compoundscorresponding to general formula ll 14. 2-amino-4-diethylamino-anilinesulphate l5. 2-methylamino-4-diethylamino-aniline sulphate 16.2-methylsulphonamido-4-diethylamino-aniline sulphate l7.2-ethoxy-4-diethylamino-aniline hemisulphate compounds corresponding togeneral formula Ill 18. l-(4-hydroxyphenyl)-pyrrolidine l9.l-(3-chloro-4-hydroxyphenyl)-pyrrolidine 20.1-(3-methyl-4-hydroxyphenyl)-pyrrolidine 21.l-(3,5-dimethyl-4-hydroxyphenyl)-pyrrolidine 22.l-(3-amino-4-hydroxyphenyl)-pyrrolidine 23.l-(3-methoxy-4-hydroxyphenyl)-pyrrolidine 24. l-(3-methylsulphonamido-4-hydroxyphenyl)- pyrrolidine 25.l-(3-acetylamino-4-hydroxyphenyl)-pyrrolidine 26. 6-amino-l,2,3,4-tetrahydroquinoline 27. 6-hydroxy-1,2,3,4-tetrahydroquinoline 28.l-ethyl-6-hydroxy-1,2,3,4-tetrahydroquinoline chlorohydrate 29.1-(4-sulphobutyl)-6-hydroxy-l ,2,3 ,4- tetrahydroquinoline 30.9-amino-julolidine sulphate N'-tetraethyl-phenylene diamine 31.l-methyl-6-amino-l ,2,3,4-tetrahydroquinoline oxalate 32.l-(2-methylsulphonylamino-ethyl)-6-hydroxy- 1,2,3 ,4-tetrahydroquinoline33. 1-(2-hydroxyethyl)-6-hydroxy-1,2,3 ,4- tetrahydroquinoline 34.1-(4-sulphobutyl)-6-amino-l ,2,3 ,4-

tetrahydroquinoline 35. 9-hydroxy-julolidine.

The p-phenylene diamine and p-aminophenol compounds of use according tothe present invention can be prepared as known in the art, e.g. asdescribed in U.S. Pat. No. 3,265,499 of Jozef Frans Willems,

George Frans Van Veelen and Louis Maria De Haes issued Aug. 9, 1966 andU.S. Pat. No. 3,265,502 of Jozef Frans Willems and George Frans VanVeelen issued July 8, 1966, in United Kingdom Pat. specifications, No.928,671 filed Feb. l9, 1960 by llford Ltd. and No. 858,432 filed Mar. 5,1958 by Imperial Chemical lndustry and in Belgian Pat. specification No.715,500 filed May 22, 1968 by Gevaert-Agfa N.V.

In accordance with the present invention there is provided a process ofmaking photographic records which comprises treating a photographicmaterial having layers containing developable silver salts with anaqueous alkaline solution in the presence of a hydroxylamine developingagent and a p-phenylene diamine or p-aminophenol compound as describedabove. The invention also includes developer compositions comprising inaddition to a hydroxylamine developing agent, a p-phenylene diamine orp-aminophenol compound as described. By hydroxylamine developing agentit is intended to embrace hydroxylamine itself as well as derivativesthereof as described above. The pphenylene diamine and p-aminophenolderivative of use according to the present invention may be added to thedeveloping bath or to the emulsion or to both simultaneously, theprocessing bath being preferred, however.

Developer compositions that comprise the superadditive developing agentsaccording to the present invention may comprise in addition thereto anyof the common ingredients employed in developing compositions, e.g.,alkalies such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, trisodium phosphate etc., silver halide solvents such assodium thiosulphate, sodium thiocyanate and cyclic imides such asbarbiturates or uracils, preservatives such as sulphites, bisulphites,metabisulphites and acids such as boric acid and citric acid. Furtherthe developer composition may comprise potassium bromide andwater-softening agents such as polyphosphates and derivatives ofethylene diamine tetraacetic acid, antifoggants such as benzotriazole,S-nitrobenzotriazole and 6- nitrobenzimidazole and wetting agents aswell as other compounds known in the photographic development techniquesuch as development restrainers and development accelerators.

The ratio of hydroxylamine developing agent to pphenylene diamine orp-aminophenol compound used in the present invention can be chosen insuch a way that the combination is suited for the development of allkinds of materials including materials having silver chloride emulsionlayers of low sensitivity as well as materials having highly sensitivesilver bromo-iodide emulsion layers. This ratio may vary within widelimits and also depends on the particular hydroxylamine developing agentused. In most cases the ratio is chosen in such a way that the amount ofthe hydroxylamine developing agent strongly outweighs the p-phenylenediamine or p-aminophenol compound.

A strong superadditive effect is obtained by using an amount of 0.05 to10 millimole preferably from 0.3 to 6 millimole of p-phenylene diamineor p-aminophenol derivative to an amount of 10 to millimole ofhydroxylamine developing agent, per liter of developing composition. Ofcourse larger amounts of said pphenylene diamine or p-aminophenolcompounds can be used, although the superadditive effect obtained withhigher concentrations is not more considerable.

The novel combination of developing agents of the invention may be usedin conventional or wet development of silver halide emulsions, indiffusion transfer processes, both dye and silver, in such photographicprocesses known as stabilization processing wherein it is desired toeliminate or minimize the need forwashing or stabilizing operations inliquid baths subsequent to the formation of the silver print, etc.

In diffusion transfer processes, as is well known in the art, an exposedsilver halide emulsion is treated with a liquid processing compositionwhile in superposed relationship with an image-receiving material. Bythis treatment the exposed silver halide is developed to silver and theunexposed silver halide is converted into a complex silver salt which istransferred to the imagereceiving material and there reduced to silverto form a positive print. The processing composition normally includes asilver halide solvent, such as sodium thiosulphate, sodium thiocyanateand cylic imides such as barbiturates or uracils, which forms withsilver halide a soluble complex as is well known in the art of formingsilver images by transfer, and may also include a film-forming materialsuch as sodium carboxymethylcellulose and hydroxyethylcellulose, starchor gum for increasing the viscosity of the composition as, for'instance,in the case of in-camera silver complex diffusion transfer processing.

In stabilization processing the time-consuming fixing and washingoperations are eliminated in order to produce the photographic record inthe least possible time by converting after development, with the aid ofstabilizing agents such as ammonium thiocyanate, the unexposed andundeveloped silver halide of the photographic emulsion into colorlesslight-insensitive compounds that need not be removed by washing.

The developing agents of use according to the invention may be employedin solution or they may be initially incorporated in a layer of thephotosensitive material, e.g., a silver halide emulsion layer or another colloid layer in water-permeable relationship therewith. in silvercomplex diffusion transfer processes they may also be incorporated in alayer of the image-receiving material which, during processing, is insuperposed relationship with the photosensitive silver halide material.

The following examples illustrate the present invention.

Example 1 sodium sulphite 100 g sodium hydroxide g S-nitro-benzotriazole80 mg potassium bromide 1g hydroxylamine hydrochloride 0.06 mole waterto make 1 liter The other strips are developed in baths having the samecomposition as bath A but containing moreover one of the compoundslisted in the table below in the amount given.

The densities obtained are listed in the following table.

Densities obtained after a Developing bath development time of Osec20sec 1min 3min 5min Bath A 0.04 0.05 0.34 0.95 1.43 Bath A mg (0.31mmole) of compound 3 0.04 0.07 0.79 1.97 2.68 Bath A 66 mg (0.31 mmole)of compound 28 0.04 0.12 0.86 2.17 3

Example 2 This example is analogous to example 1 with the onlydifference that now a developing bath B is used which only differs frombath A in that the hydroxylamine hydrochloride has been replaced by 0.06mole of N- methylhydroxylamine hydrochloride.

The following results are attained.

Developing bath Densities obtained after a development time of Osec20sec 1min 3min 5min Bath B 0.05 0.05 0.07 0.60 1.09 Bath B +105mg(0.31mmo1e) of compound 3 0.04 0.04 0.19 1.83 2.61 Bath 13 66 mg (0.31mmole) of compound 28 0.04 0.04 0.18 1.66 2.72

Example 3 This example is analogous to example 1 with the onlydifference that now a developing bath C is used which only differs frombath A in that the hydroxylamine hydrochloride has been replaced by 0.06mole of N,N- diethylhydroxylamine oxalate.

The following results are attained.

This example is analogous to example 1 with the only difference that nowa developing bath D is used which only differs from bath A in that thehydroxylamine hydrochloride has been replaced by 0.06 mole of N-methyl-N-(2-hydroxy-3-diethylaminopropyl) hydroxylamine.

The following results are attained.

Developing bath Densities obtained after a development time of sec 20sec1min 3min 5min Bath D 0.04 0.04 0.04 0.1 l 0.56 Bath D +105 mg (0.31mmole) of compound 3 0.04 0.04 0.17 1.33 2.15 Bath D 66 mg (0.31 mmole)of compound 28 0.04 0.04 0.12 1.01 1.97

Example 5 This example is analogous to example 1 with the onlydifference that now a developing bath E is used which only differs frombath A in that the hydroxylamine hydrochloride has been replaced by 0.06mole of the hydroxylamine derivative corresponding to the formula:

according to the co-pending application filed on even date herewith forNovel Photographic Developers.

This example is analogous to example 1 with the only difference that nowa developing bath F is used which only differs from bath A in that thehydroxylamine hydrochloride has been replaced by 0.06 mole of thehydroxylamine derivative with formula:

zmcQ-s 01' according to the co-pending application filed on even dateherewith for Novel Photographic Developers."

The following results are attained.

Developing bath Densities obtained after a development time of Osec20sec 1min 3min 5min Bath F 0.04 0.50 1.13 2.19 3 Bath F +105 mg (0.31mmole) of compound 3 0.04 0.71 1.35 2.91 3 Bath F 66 mg (0.31 mmole) ofcompound 28 0.04 0.73 1.35 2.60 3

Example 7 A photosensitive element was prepared comprising on a papersupport a propylene, bromoiodide emulsion layer containing per kg anamount of silver halide corresponding to 60 g of silver nitrate.

After exposure, the photosensitive element and an image-receivingelement, which comprises a silver receptive layer containing developmentnuclei dispersed in a matrix of colloidal silica coated on awater-impervious support according to the practice described in US. Pat.No. 2,823,122 of Edwin H.Land issued Feb. 11, 1958, were advanced insuperposed relationship between a pair of pressure applying rollers tospread between them in a thin layer the following processingcomposition:

water ml sodium carboxymethylcellulose 5 g sodium hydroxide 15 g uracill 1.25 g 30 ammonium hydroxide 3.5 ml N,N-diethylhydroxylamine oxalate0.06 mole l-phenyl-2-tetrazoline-5-thione 0.2 g compound 3 mg After acontact period of 36 seconds the emulsion together with the layer ofprocessing liquid was stripped from the image-receiving element touncover the positive print.

When using a same developing composition but comprising no compound 3the density of the positive print obtained was markedly lower. Moreover,in the presence of compound 3 better quality transfer images areobtained at lower illumination levels than is the case when usingN,N-diethylhydroxylamine alone.

We claim:

1. Photographic developing method which comprises the black and whitedevelopment of an exposed silver halide emulsion layer of a photographicmaterial with an aqueous alkaline composition comprising a hydroxylaminedeveloping agent and a p-phenylene diamine or p-aminophenol derivativehaving one of the formulas l, 11 and 111:

wherein:

R stands for an alkyl group,

R, stands for alkyl or an ethylene group, or a propylene group attachedto the adjacent orthocarbon atom of the benzene ring,

R: stands for alkyl, and

R stands for an alkyl group,

at most one of R and R being substituted alkyl,

wherein:

each of R and R stands for an alkyl group, and X, stands for anelectron-donating group selected from the group consisting of alkyl,alkoxy, amino, monoalkylamine, dialkylamino, acylamino, andsulphonamido,

m. 1 1 Rs wherein:

each of X and X stands for hydrogen, halogen or an electron-donatinggroup selected from the group consisting of alkyl, alkoxy, amino,monoalkylamine, dialkylamino, acylamino, and sulphonamido,

Y stands for OH or NH,, and

R stands for an ethylene or propylene group attached to the adjacentortho-carbon atom of the benzene ring, and

R stands for hydrogen, an alkyl group or has the same significance asR,, or

R together with R and the N-atom to which they are attached from apyrrolidine ring.

2. Photographic developing method according to claim 1, wherein saidmethod is used for making images according to the silver complexdiffusion transfer process.

3. Photographic developing composition for the black and whitedevelopment of an exposed silver halide emulsion layer of a photographicmaterial comprising in aqueous alkaline solution an hydroxylaminedeveloping agent and a p-phenylene diamine or paminophenol derivativehaving one of the formulas I, ll and Ill:

II. R

wherein:

each of R, and R, stands for an alkyl group, and X stands for anelectron-donating group selected from the group consisting of alkyl,alkoxy, amino, monoalkylamine, dialkylamino, acylamino, andsulphonamido,

III. R: R5

wherein:

each of X and X stands for hydrogen, halogen or an electron-donatinggroup selected from the group consisting of alkyl, alkoxy, amino,monoalkylamine, dialkylamino, acylamino, and sulphonamido,

Y stands for OH or NH,, and

R stands for an ethylene or propylene group attached to the adjacentortho-carbon atom of the benzene ring, and

R stands for hydrogen, an alkyl group or has the same significance as Ror R together with R and the N-atom to which they are attached from apyrrolidine ring said p-phenylene diamine or p-aminophenol derivativebeing present in an amount of from 0.05 to 10 millimoles per 10 tomillimoles of hydroxyl amine developing agent per liter of developingcomposition.

4. Photographic developing method according to claim 1, wherein one ofsaid hydroxylamine developing agent and said p-phenylene diamine orp-aminophenol derivative is initially present in said photographicmaterial and transferred to said aqueous alkaline composition therefrom.

S. The photographic developing method of claim 1 wherein saidp-phenylene diamine or p-aminophenol derivative has the formula:

wherein:

R, stands for an alkyl group,

R, stands for alkyl or an ethylene group, or a propylene group attachedto the adjacent orthocarbon atom of the benzene ring,

R, stands for alkyl, and

R, stands for an alkyl group,

at most one of R and R being substituted alkyl.

6. The photographic developing method of claim 1 wherein saidp-phenylene diamine or p-aminophenol derivative has the formula:

II. R5 Rs l K l, N111 wherein:

each of R and R stands for an alkyl group, and X, stands for anelectron-donating group selected from the group consisting of alkyl,alkoxy, amino, at most one of R and R being substituted alkyl.monoalkylamine, dialkylamino, acylamino, and 9. Photographic developingcomposition of claim 3 sulphonamido. wherein said p-phenylene diamine orp-aminophenol 7. The photographic developing method of claim 1derivative has the formula: wherein said p-phenylene diamine orp-aminophenol derivative has the formula: II.

III R1 Ra in -Xa wherein: wherein:

each of X and X stands for hydrogen, halogen or an h f R nd R st nds f ran lk l roup, and

electron-donating group l t d fr t g p X stands for an electron-donatinggroup selected consisting of alkyl, alkoxy, amin m from the groupconsisting of alkyl, alkoxy, amino, kylamine, dialkylamino, acylamino,and monoalkylamine, dialkylamino, acylamino, and sulphonamido,sulphonamido. Y stands for OH 01' NH and 10. Photographic developingcomposition of claim 3 R stands for an ethylene 0r pr pyl n g p whereinsaid p-phenylene diamine or p-aminophenol tached to the adjacentortho-carbon atom of the d i i h h f l benzene ring, and R stands forhydrogen, an alkyl group or has the R7 R8 same significance as R or Rtogether with R and the N-atom to which they are attached from apyrrolidine ring.

8. Photographic developing composition of claim 3 wherein saidp-phenylene diamine or p-aminophenol X derivative has the formula:

I. R1 R9 3 -wherein:

each of X and X stands for hydrogen, halogen or an electron-donatinggroup selected from the group consisting of alkyl, alkoxy, amino,monoal- N kylamine, dialkylamino, acylamino, and 40 sulphonamido, Ra Ystands for OH or Nl-l and wherein: R stands for an ethylene or propylenegroup at- R stands for an alkyl group, tached to the adjacentortho-carbon atom of the R stands for alkyl or an ethylene group, or abenzene ring, and

propylene group attached to the adjacent ortho- R stands for hydrogen,an alkyl group or has the carbon atom of the benzene ring, samesignificance as R,, or R stands for alkyl, and R together with R and theN-atom to which they are R stands for an alkyl group, attached from apyrrolidine ring.

t k k 1!

2. Photographic developing method according to claim 1, wherein saidmethod is used for making images according to the silver complexdiffusion transfer process.
 3. Photographic developing composition forthe black and white development of an exposed silver halide emulsionlayer of a photographic material comprising in aqueous alkaline solutionan hydroxylamine developing agent and a p-phenylene diamine orp-aminophenol derivative having one of the formulas I, II and III: 4.Photographic developing method according to claim 1, wherein one of saidhydroxylamine developing agent and said p-phenylene diamine orp-aminophenol derivative is initially present in said photographicmaterial and transferred to said aqueous alkaline composition therefrom.5. The photographic developing method of claim 1 wherein saidp-phenylene diamine or p-aminophenol derivative has the formula:
 6. Thephotographic developing method of claim 1 wherein said p-phenylenediamine or p-aminophenol derivative has the formula:
 7. The photographicdeveloping method of claim 1 wherein said p-phenylene diamine orp-aminophenol derivative has the formula:
 8. Photographic developingcomposition of claim 3 wherein said p-phenylene diamine or p-aminophenolderivative has the formula:
 9. Photographic developing composition ofclaim 3 wherein said p-phenylene diamine or p-aminophenol derivative hasthe formula:
 10. Photographic developing composition of claim 3 whereinsaid p-phenylene diamine or p-aminophenol derivative has the formula: